Disazo dyestuffs



United States Patent 2,760,958 nrsAzo DYESTUFFS Werner Bossard, Riehen, near Basel, Switzerland, and Paul Dussy, St. Louis, France, assignors to J. R. Geigy A.-G., Basel, Switzerland, a Swiss firm No Drawing. Application December 7, 1954, Serial No. 473,722

Claims priority, application Switzerland December 9, 1953 9 Claims. (Cl. 260-175) The present invention concerns new disazzo dyestuffs which are distinguished by their very pure orange to red shades on cellulose fibres, the direct cellulose dyeings of which have, relatively, a very good fastness to light. It further concerns processes for the production of these disazo dyestuffs as well as their use for the dyeing of cellulose material and also the material dyed in pure shades with the help of these dyestuffs.

It has been found that new, very pure and substantive disazo dyestuffs are obtained if 1 mol of 5.5'-dihydroxy- 2.2-dinaphthyl urea7.7-disulphonic acid is coupled in steps in any order desired with the equimolecular amount of a diazotised amino compound of the general Formula I:

HO- NH-O 0- 11000 I and with the equimolecular amount of a diazotised aminoaryl sulphonic acid of the benzene or naphthalene series. In the above formula X represents hydrogen, halogen, an alkyl or a sulphonic acid group and the benzloyl radical may contain further non-ion-cgenic subs-tituents but, however, no groups capable of forming a metal complex.

The amino compounds of the general Formula I usable in the process according to the present invention are obtained from S-amin-o-Z- hydroXybenZene-l carboxylic acids which may be further substituted in the 3-position of the benzene ring by halogen, an alkyl ora sulph'onic acid group, by acylating with an mor p-nitrobenzoyl halide which can contain further non-ionogenic substituents such as, e. g. halogen lOI alkyl groups but, however, no groups capable of forming a metal complex, and then reducing the nitro group to the amino group. The disazo dyestufis according to the present invention derived from p-aminobenzoyl compounds of the general Formula I have, in general, a better atfin-ity to cellulose and are to be preferred for this reason. The amines of the general Formula I are diazotised tor example by the indirect method in cold mineral acid by the dropwise addition of the aqueous solution of the alkali salts containing sodium nitrite.

Other diazo components which can be used in the process according to the present invention are aminobenzene and aminonaphthalene sulphonic acids, both the monoas well as the poly-sulphonic acids, e. g. 2-, 3- or 4-amino'benzene4l-sulphonic acid, 5-amino-2-methylbenzene-l-sulphonic acid, 1-amino-4-methoxybenzene-2- sulphonic acid, 1-amino 4'ethoxybenzene-2 sulphonic acid, 1-amino 2.4-dichlorobenzene-6-sulphonic acid, 1- arnin-o-ZA-dimethylbenzene-G-sulphonic acid, l-aminobenzene-2.4- or -2.5-disulphonic acid, l-aminonaphthalene-3-, -4-, -5-, -6-, -7- or -'8-sulphonic acid, l-aminonaphthalene-3.6- or -3.8-disulphonic acid, 2-aminonaphthalene-5-, -6-, -7-, or -8- sulphonic acid, Z-aminonaph- 2,760,958 Patented Aug. 28, 1956 fore, to be preferred. The amino aryl sulphonic acids are diazotised by methods known per so with alkali nitrite in mineral acid aqueous solution or suspension in the cold.

The 5.5 dihydroxy 2.2 dinaphthyl urea 7.7- disulphonic acid can be coupled advantageously in alkaline, neutral to acid solution of its alkali salts in the cold. Often it is of advantage first to react the diazotised aminoaryl sulphonic acid in the presence of alkali acetates and then react the diazo compound corresponding to the general Formula I in the presence of alkali carbonates or bicarbonates. The disazo dyestuffs formed are isolated by known methods by precipitation with sodium chloride, filtration and drying.

In the form of their alkali salts which dissolve well in water, the new disazo dyestuffs are red to dark redbrown powders according to the composition. They dissolve in water with an orange to redsh'ade and dye cellulose material from a dyebath containing Glaubers salt in very pure similar shades. Particularly valuable disazo dyestuffs are obtained from diaz 'otised amino compounds of the general Formula H HO O Y (II) wherein one Y represents the primary amino group, the other Y represents hydrogen or the methyl group and X has the meaning given in Formula I. The disazo dyestuffs according to the present invention can also be treated with agents giving off metal, e. g. with agents giving off chromium or copper. The treatment is performed preferably on the fibre so that the wet fastness properties of the direct cellulose dyeings can be even further improved. However, the metallisation causes an undesirable dullness of the shades so that non-metallised cellulose dyeings are to be preferred.

The following examples illustrate the invention without limiting it in any way. Where not otherwise stated, the parts are given as parts by Weight. The temperatures are in degrees centigrade. I

7 Example 1 30.3 parts of. .Z-naphthylamine disulphonic acid-(6.8) are dissolved at 7080 in 320 parts of water and the amount of sodium carbonate necessary to make the reaction neutral. After cooling to room temperature, 6.9 parts of sodium nitrite and 30 parts of a 30% hydrochloric acid are added. The diazo solution so prepared is poured into a 20 warm solution of 50.4 parts of the symmetrical urea of 2-amino-S-hydroxynaphthalene sulphonic acid-( 7) and 16 parts of sodium acetate in 800 parts of water. After 4-6 hours, the unilateral coupling is complete. The dyestuif solution is heated to 4045, neutralised by the addition of 8.3 parts of sodium carbonate and 40 parts of sodium carbonate are added.

29.1 parts of 5-(3-methy1-4f-aminobenzoylamino)-2- hydroxybenzene-l-carboxylic acid are dissolved in the warm in 350 parts of Water with the addition of 4 parts of caustic soda. After the addition of 7.2 parts of sodium nitrite, the solution is cooled and stirred at room temperature into a mixture of 45 parts of 30% hydrochloric acid and 100 parts of water. The yellow diazo compound precipitates and, after 2 hours, it is coupled with the monoazo solution described above. After stirring for a consider able time at 4045, the coupling is complete. The dyestutl is precipitated hot with a little salt, and filtered oil at room temperature. The dried dyestuif of the formula:

l H as- O H is a brown-red powder which dissolves in water with a yellowish-red and in concentrated sulphuric acid with a violet colour. It dyes cellulose fibers in pure bluish scarlet shades which have very good fastncss to light, alkali and acid.

It in the above example, 29.l parts of -(3-1nethyl-4- aminobenzoylamino-Z-hydroxybenzene-l-carboxylic acid are replaced by the number of parts of a diazo component given in the table below, dyestulis with the following properties are obtained.

N0. oi Diazo component coupled with Resulting dye- Dyestufl parts the monoazo dyestufi from. 30.3 stufi: P=colour N 0. by parts of 2-uaphthyla1nine-6.S- of powder; S=

Weight disulplaonic acid and 50.4 parts shade of celluoi J-acid urea lose dyeing 1 27. 8 5 (4 aminobenzoylamino) 2 P=bordeaux;

hydiroxybenzene 1 carboxylic S=scar1et. act:

2. 27. 8 5 (3 aminobenzoylamino) 2 P=brown red;

hydroxybenzene 1 carboxylic S=scarlet. ac.

3. 29. 1 5 (4 methyl 3 aminobenzoyl- P=red-brown; amino) 2 hydroxybenzene l S=brill. red. carboxylic acid.

4 31.2 5 (4 ehloro 3 arnlnobenzoyl- P=brown; 8:

amino) 2 hydroxybenzene 1 red. carboxylic acid.

5. 35. 9 5 (4 aminobenzoylamino) 2 P=red; S=

hydroxybcnzene l carboxylic scarlet. acid-3-sulphonic acid.

6.. 31. 2 5 (3 aminobenzoylamino) 2 P=brown; S=

hydroxy 3 chlorobenzene 1- red. carboxylic acid.

7 29.1 5 (4 aminobenzoylamino) 2 P=brown; S=

hydroxy 3 methyl benzene scarlet. l-carboxylic acid.

8. 30. 6 5 (3 -mcthyl 4 aminobenzoyl- P=red; S= amino) 2 hydroxy 3 methylbrill. red. benzene-l-carboxylic acid.

9. 31. 2 5 (2 chloro 5 aminobenzoyl- P=brown red;

amino) 2 hydroxybenzene 1 S =red. carboxylic acid.

10.- 31.2 5 2 chloro 5 aminobenzoyl- P=bordeaux;

amino) 2 hydroxybenzene 1 S =red. carboxylicacid-3 -sulphonicaeid.

11 36. 2 5 (2.4 diohloro 5 aminoben- P=brown; S=

zoylammo) 2 hydroxy 3 red. mectlhylbenzene 1 carboxylic ac 12 32. 6 5 (3 methyl 4 aminobenzoyll? brown-red;

amino) 2 hydroxy 3 chloro- S=red. benzene-l-carboxylic acid.

Example 2 30.3 parts of 2-naphthylamine-4.S-disulphonic acid in 350 parts of water are diazotised at room temperature with 6.9 parts of sodium nitrite and parts of 30% hydrochloric acid. The diazo suspension so obtained is added to a solution of 50.4 parts of the symmetrical urea of 2- amino-5-hydroxynaphthalene-7-sulphonic acid and 16 parts of sodium acetate in 800 parts of water. The formation of the monoazo dyestuff is completed after 46 hours whereupon the solution is heated to id-45, neutralised with 8.3 parts of sodium carbonate and parts of sodium bicarbonate are added.

7.2 parts of sodium nitrite are added at room temperature to a solution cooled to 20 of 27.8 parts of 5-(4-zuninobenzoylarnino) -2-hydroXybenzene-l -carboxylic acid which have been dissolved by Warming in 490 parts of water with the addition of. 4 parts of caustic soda. The whole is then l l I OH O H;

COOH

added dropwise to a mixture of 45 parts of 30% hydroohloric acid and parts of water. The diazotisation is complete in 1 /2 to 2 hours whereupon the yellow diazo suspension is stirred into the monoazo dyestui'f solution described above. After 10 hours, the diaso dyestufi is precipitated hot with a little salt, filtered off and dried. it is a bordeaux red powder which dissolves in water with a yellowish-red and in concentrated sulphuric acid with a violet colour. The dyestul'i of the formula QOH COOH

dyes fibres of natural or regenerated cellulose in scarlet r red shades which have really good fastuess to light.

If in the above example, the 30.3 parts of Z-naphthylamino-4.8-disulphcnic acid are replaced by the number of parts of a naphthylamine mono-, dior tri-sulphonic acid given in the table below, then dyestuffs with the following properties are obtained.

Diazo component coupled with 50.4 Resulting dye- Dye- No. of parts of the symmetrical urea of 2- stuff: stufi parts amino-fi-hydroxynaphathalene-7- colour of N o. by sulphonic acid and with 27.8 parts powder; 5: weight of 5-(4-aminobcnzoyl-amino)-2- shade of Dyehydroxybenzene-1-carboxylic acid ing on Cotton 1 22.3 1 -a1ninonaphthalene 6 sulphonic P=red; S=

aci scarlet. 2 23. 3 l-aminonaphthalcne 7 sulphonic l=orangeacid. red; S=

scarlet. 3 22.3 Z-aminonaphthalene 1 sulphonic P=hrown red,

acl S=orange red. 4-. 22. 3 2 -aminonaphthalene 6 -sulphonic P=red; S=

aci orange red. 5 22. 3 Z-aminonaphthalene-S sulphonic P=red; S=

aci orange red. 6. 30. 3 l-aminonaphthalene-3.6-disulphonic P=red brow-n;

aci S=scarlet. 7 30. 3 l-aminonapthalene-afi' disulphonie P=brownacid. violet; S=

. scarlet. 8 30. 3 2-amiuonaphthalene-5.7- disulphonic P=brown red;

aci S=scarlet. 9. 30. 3 2-ami11onaphthalene-3.6disulphonic P =bordeaux;

a S=scnrlet. l0 38. 3 1 aminonaphthalene 3.6.8 trisul- P=brownphonic acid. viglet; S=

re 11 38. 3 2 aminonaphthalene 1.5.7 trisul- P=brownphonic acid. violet; S=

red.

If in Example 2, 27.8 parts of 5-(4-am1nobenzoylammo).-2-hydroxybenzene-l-carboxylic acid are replaced by the number of parts of a diazo component given in the table below, then dyestufis with the following properties are obtained.

No. of Diazo component coupled with Resulting dye- Dyestufl parts the monoazo dyestufi from 30.3 stufizP=colour No. by parts'oi 2-naphthylamme-4.8-diof powder; S=

weight sulphonic acid and 50.4 parts of shade of cellu- J -acid urea lose dyeing 1 29.1 5 -(3-methyl -4-aminobenzoy1- P=brown red;

amino) 2 hydroxybenzene 1 S =scar1et. carboxylic acid.

2 27. 8 5 (3 aminobenzoylaminc) 2 P=brown red;

hygroxybenzene 1 carboxylic S=scarlet. ac1

3 35.9 5 (4 aminobenzoylamino 2 P=red; S=

hydroxybeuzene 1 carboxylic scarlet. acid 3 sulphonic acid.

4 29. 1 5 (4' aminobenzoylamino) 2 P=red brown;

hydroxy 3 methylbenzene 1 S =red. carboxylic acid.

6 30. 6 5 (3 methyl 4 aminobenzoyl- P=red; S= amino) 2 hydroxy 3 methylbrilliant red. benzene 1 carboxylic acid.

Example 3 27.2 parts of 5-(4'-aminobenzoylamino)-2-hydroxybenzene-l-carboxylic acid are dissolved at 60-70 in 400 parts of water with 4 parts of caustic soda and the solution is cooled to room temperature. 6.9 parts of sodium nitrite are added to the solution and the whole is added dropwise at 2025 to a mixture of 45 parts of 30% hydrochloric acid and 100 parts of water. The diazotisation is complete after 2 hours. The yellow diazo suspension is added at 20-25 to a solution of 50.4 parts of 5.5-dihydroxy-2.2' dinaphthyl urea-7.7'-disulphonic acid and 16 parts of sodium acetate in 800 parts of water. After 4-6 hours the unilateral coupling is complete whereupon the dyestutf solution is heated to 40-45,

neutralised with 7.5 parts of sodium carbonate and 40 parts of sodium bicarbonate are added.

20.5 parts of l-amino-2.4-dimethylbenzene-6-sulphonic acid are diazotised at -5 with 7.0 parts of sodium acid given in thetable. below, then dyestuifs with the following properties are obtained.

Diazo component coupled with the monoazo dyestufi from 27.2 parts or 5-(4-an1inobenzoylamino) -2-hydroxybenzene-l-carboxylic acid and 50.4 parts of the symmetrical urea of 2-amino-5-hydroxynaphthalene-7-sulphonic acid No. of parts Resulting dyestufi; P=colour of powder; S shade of cellulose dyeing Dyestuff S No. weight l-amino-2.4-dich1orobenzene-6-sulphonic acid. l-aminobenzene-Z-sulphonic acid.

1 -aminobenzene-4-sulphonic acid 1 -a1mno -4-methoxybenzene -2-sulphonic acid.

1 amino 4 ethoxybenzene 2 sul phonic acid.

1-aminobenzene-2.5-disu1phonic acid 1mug:o-4-chlorobenzene-S-sulphonic ac 4-amino -1.1' -diphenyIether-3-sulphonic acid. l-aminobenzene-2.4-disulphonic acid Example 4 1 part of the dyestufI obtained according to example 1 is dissolved in a .dyebath containing 3000 parts of water and 3 parts of sodium carbonate. 100 parts of cotton are entered at 40-50", the bath is heated within 30 minutes to 90-95 parts of sodium sulphate are added and dyeing is performed for 60 minutes at this temperature. The goods are then rinsed with cold Water and dried in the usual way. The cotton is dyed in brilliant scarlet shades which have good fastness to light.

What we claim is: 1

1. A disazo dyestufi of the general formula:

SOIH X OH JOOH wherein A represents an aromatic radical selected from the group consisting of the benzene and naphthalene series, B represents an aromatic radical of thebenzene series in which the bonds shown stand in other than the nitrite in 300 parts of water bythe quick addition of o-position of said aromatic residue and which is free 200 parts of 30% hydrochloric acid. After 1 hour, the diazo suspension so obtained is stirred into the monoazo solution above described. After 10-12 hours, the disazo dyestuff is heated to 80-85 precipitated with salt, filtered oif and dried at 80. dissolves in water with an orange and in concentrated Hols NEOONH I S0aH I X H OH Y l sulphuric acid with a blue-violet colour. The dyestuff of the formula:

OOH

from ionogenic substituents and groups capable of forming metal complexes, X represents a member selected from the group consisting of hydrogen, chlorine, methyl and sulphonic acid groups, n is an integer from 1 to 3 in- It is a red powder which elusive.

2. A disazo dyestufi of the general formula:

Coon

wherein A represents an aromatic radical selected from the group consisting of the benzene and naphthalene -SOaH SOaH wage... C Hz 3. A disazo'dyestufi of-ithe general formula:

Y OOOH' wherein X represents a member selected from the group consisting of hydrogen, chlorine, methyl and sulphonic acid groups, Y represents-a member selected from the group consisting of H, Cl and CH3, m is an integer from 2 to 3 inclusive.

5. A disazo dyestufi of the formula:

6. A disazo dyestufi of the formula:

7. A disazo dyestufi of the formula:

8. A disazo dyestufi of the formula:

s og]: Hots nN-c-o-nrr SOaH no=s N=N N=NGGOHNQ-OH n on 00H 9. A disazo dyestuflf of the formula:

No references cited. 

1. A DISAZO DYESTUFF OF THE GENERAL FORMULA: 